Method for making multifunctional materials

ABSTRACT

The invention relates to a method of making multifunctional materials, especially materials comprising at least one primary carbamate group and a grafting moiety (cii). The method of the invention requires the successive or simultaneous reactions of a material P with a grafting material (c) and ammonia. Material P comprises two or more cyclic carbonate groups (bi). Grafting material (c) comprises at least one amine group (ci) and a grafting moiety (cii). The amine group (ci) is selected from primary amines, secondary amines, and mixtures thereof. The resulting multifunctional materials are useful in a variety of curable coating compositions, including solventborne, waterborne, electrodeposition, liquid solvent free coatings, powder, and powder slurry.

FIELD OF THE INVENTION

[0001] This application claims the benefit of prior U.S. applicationSer. No. 09/998,365, filed Nov. 29, 2001.

[0002] The invention relates to methods of making thermosettingmultifunctional materials, especially those materials comprising atleast one primary carbamate group and most particularly tomultifunctional materials comprising at least one β or higher-hydroxyprimary carbamate functional group.

BACKGROUND OF THE INVENTION

[0003] Graft polymers have been known for use in the coatings industryas binders for thermosetting compositions. Graft polymer binderstypically have a plurality of functional sites reactive with thefunctional sites of one or more crosslinking agents and upon cure,produce hard, durable, glossy films suitable for use in a variety ofcoating applications. Preferred applications include automotive primers,basecoats, and clearcoats. Such coatings may be waterborne,solventborne, powder, or combinations thereof.

[0004] The manufacture of graft polymers has typically involved theproduction of a base material having one or more functional sites permolecule. At least one of these functional sites must be capable ofsubsequent or concurrent reaction with at least one functional group ofa graft moiety.

[0005] Graft copolymerization processes have traditionally been used toincorporate moieties that cannot be incorporated during the preparationof the base material. Examples of such moieties include polymers such aspolyesters, polyurethanes and the like, surfactants, halogenatedcompounds, certain water dispersible groups such as nonionic groups,simple alkyl groups, functional groups such as beta- and higher hydroxyprimary carbamate groups, including gamma-hydroxy primary carbamategroups, delta-hydroxy primary carbamate groups, and the like, thederivatives thereof, acid functional materials, epoxy functionalmaterials, silane functional materials, siloxane functional materialsand the like.

[0006] However, numerous problems occur during such prior art graftreaction processes. In particular, in the processes of the prior art,the reaction of the graft moiety and the base material results inreaction products which are reactive with one or more species, includingthe base material, other intermediate species, and/or the graft moiety.Such undesirable side reactions result in uncontrolled molecular weightgrowth, the loss of desired functionality, and/or gelation.

[0007] In addition, the uncontrollable reactivity of the functionalgroup used as the grafting site on the base material can often limit theuse of additional functionality on the base material and hinder theproduction of multifunctional graft materials. As a result, it has beendifficult to obtain certain multifunctional graft materials using theprocesses of the prior art.

[0008] For example, if an epoxy group is used as the grafting site on anacrylic backbone, ethylenically unsaturated monomers having functionalgroups reactive with epoxy must be avoided during the polymerization ofthe acrylic backbone if the epoxy group results from the use of anethylenically unsaturated monomer such as glycidyl methacrylate.Illustrative functional groups that would have to be avoided includeactive hydrogen containing groups such as amine functional ethylenicallyunsaturated monomers, acid functional ethylenically unsaturatedmonomers, and depending, on the polymerization conditions, hydroxycontaining ethylenically unsaturated monomers.

[0009] Assuming that an acrylic backbone polymer's functionality islimited to epoxy groups, the use of amine, hydroxy, or acid functionalgraft moieties will result in a variety of intermediate species whichare reactive with the graft moiety, the epoxy functionality of theacrylic backbone or both. As a result, attempts to use an amine or acidfunctional graft moiety will often lead to uncontrolled molecular weightgrowth, the loss of desired functionality on the backbone, and/orgelation.

[0010] Moreover, it would be advantageous to obtain graft materials withthe aforementioned advantages but which also comprise primary carbamategroups. Graft materials containing mixed functional groups such as β orhigher-hydroxy primary carbamate groups would be even more advantageous.

[0011] It would thus be advantageous to provide a method of graftingthat would address the deficiencies of the prior art. In particular,what is desired is a method of graft polymerization that wouldfacilitate the production of multifunctional graft materials, especiallymultifunctional graft polymers wherein at least one functional groupcomprises a primary carbamate group, especially a β or higher-hydroxylprimary carbamate group. Such improved graft material manufacturingprocesses would have a decreased risk of uncontrolled molecular weightgrowth, the loss of desired functionality on the base material, and/orgelation.

[0012] It is thus an object of the invention to provide a method ofmaking multifunctional graft materials that eliminates the disadvantagesof the prior art.

[0013] In particular, it is an object of the invention to provide amethod of obtaining a graft material having at least two functionalgroups that would be reactive with each other under reaction,oligomerization, or polymerization conditions. That is, the at least twofunctional groups on the final reaction product would normally presentserious challenges with respect to side reactions if incorporated viatraditional reaction, oligomerization or polymerization routes.

[0014] It is another object of the invention to provide a relativelysimple and commercially feasible method of making β or higher-hydroxyprimary carbamate functional materials having at least one otherfunctional group obtained through grafting reactions, most particularlyat least one hydroxyl functional urethanized grafting moiety.

SUMMARY OF THE INVENTION

[0015] These and other objects have been achieved with the methods ofthe invention.

[0016] In one embodiment, the method of the invention provides a simpleand commercially feasible way of making multifunctional materials. Theterm “multifunctional material” as used herein refers to compounds,oligomers, or polymers comprising a least one primary carbamate groupand at least one grafting moiety (cii) per molecule on average. In amost preferred embodiment, ‘multifunctional material’ refers tocompounds, oligomers, or polymers comprising one or more β or higherhydroxy primary carbamate groups and one or more hydroxyl functionalurethanized grafting moieties (cii) per molecule on average.

[0017] It is an aspect of the method of the invention that a basematerial P comprising two or more cyclic carbonate groups (bi) permolecule on average must undergo two different reactions, eithersuccessively or simultaneously. More particularly, at least one of thecyclic carbonate groups on average per molecule of the base material Pmust undergo a reaction (A) with ammonia. At least one other cycliccarbonate group of the base material P per molecule on average mustundergo a reaction (B) with a grafting material (c).

[0018] Grafting material (c) comprises at least one amine group (ci) anda grafting moiety (cii). The amine group (ci) is selected from primaryamines, secondary amines, and mixtures thereof. Grafting moiety (cii)may be a material, oligomer, or polymeric in nature. Grafting moiety(cii) will generally comprise a backbone which may be aliphatic,cycloaliphatic, aromatic, unsaturated and mixtures thereof. Graftingmoiety (cii) may also contain hetroatoms such as O, S, N, Si, and thelike which may be in the form of ether groups, ester groups, urethane(non-primary carbamate) groups, urea groups, mixtures thereof and thelike. Grafting material (c) can possess additional functional groups(cii_(fg)) that are not reactive towards a cyclic carbonate group underthe conditions of reactions (A) or (B). Non-limiting examples ofadditional functional groups (cii_(fg)) are carbamate groups, acidgroups, hydroxy groups, ethylenically unsaturated groups, ester groups,ether groups, urethane groups, urea groups and mixtures thereof.

[0019] In another embodiment, the method of the invention providesmultifunctional waterborne materials, especially β or higher-hydroxyprimary carbamate functional materials. In this embodiment, the at leastone grafting moiety (cii) is selected from secondary amines, tertiaryamines, acid groups, salted acid groups, and nonionic groups. Inaddition, it is an aspect of this embodiment of the invention that ifthe at least one grafting moiety (cii) is a secondary or tertiary amine,or if the at least one grafting moiety (cii) is an acid group and thereaction of material P with ammonia proceeds before the reaction ofmaterial P with grafting material (c), the method of the invention willfurther comprise reacting the grafting moiety (cii) with one or moresalting agents (f) to provide a salted site (cii*) which facilitates thedispersion of the final multifunctional material into water.

[0020] The waterborne multifunctional materials of the invention willgenerally have the structure:

(C_(graft))_(i)—P—(C_(NH3))_(j).

[0021] In this formula, P is a hydrocarbon-based material selected fromthe group consisting of compounds, oligomers, and polymers, and has anumber average molecular weight P_(MW). C_(graft) is the reactionproduct of ammonia and a cyclic carbonate functional group and has atleast one structure selected from the group consisting of of formulas(I), (II) and (III):

[0022] wherein C′ is a saturated carbon having substituents selectedfrom hydrogen and alkyl groups of from one to six carbons, R is hydrogenor an alkyl group of from one to six carbons, and c_(ii) is a graftingmoiety selected from secondary amines, tertiary amines, acid groups,salted acid groups, nonionic groups, and mixtures thereof. i and j maybe the same or different and will each be a number from 1 to about 49.C_(NH3) is the reaction product of ammonia with a cyclic carbonatefunctional group and will have a structure selected from the group offormulas (I), (II) and (III):

[0023] wherein C′ is a saturated carbon having substituents selectedfrom hydrogen and alkyl groups of from one to six carbons, and n is anumber from 0 to 6. When

WV ₁ =P _(MW)÷(i+j) and WV ₂ =P _(MW)÷(i),

[0024] the waterborne multifunctional materials of the invention will beelectrodepositable if WV₁ is a number from 500 to 2000 and WV₂ is anumber from 320 to 1000; water dispersible if WV₁ is a number from 400to 800 and WV₂ is a number from 450 to 1500; and water soluble if WV₁ isa number less than 600 and WV₂ is a number from 320 to 2500.

[0025] The invention further provides a method of making multiplemultifunctional acrylic materials from a single precursor material orlimited starting reactants. This method requires providing anethylenically unsaturated monomer mixture (a) comprising two or moremonomers (ai) having at least one cyclic carbonate group and thestructure

[0026] In this formula L is a linking group selected from aliphaticgroups, cycloaliphatic groups, aromatic groups and mixtures thereof offrom one to seven carbons, n is a number from zero to six, and R iseither hydrogen or an alkyl group of from one to six carbons.

[0027] The method then requires polymerizing the monomer mixture (a) tomake an acrylic backbone polymer (b) comprising two or more cycliccarbonate functional groups (bi) and then subjecting a first portion ofthe acrylic backbone polymer (b) to successive or simultaneous reactionsof reaction (A) with a first grafting material (c) and reaction (B) withammonia, to make a first multifunctional material of the formula:

[0028] wherein A is the residue resulting from the polymerization ofethylenically unsaturated monomers which does not contain a cycliccarbonate group, L is a linking group selected from aliphatic groups,cycloaliphatic groups, aromatic groups and mixtures thereof of from oneto seven carbons, and p is number of from 0 to 5.

[0029] C_(NH3) is the reaction product of ammonia with a cycliccarbonate functional group and will have a structure selected from thegroup of formulas (I), (II) and (III):

[0030] wherein C′ is a saturated carbon having substituents selectedfrom hydrogen and alkyl groups of from one to six carbons, and n is anumber from 0 to 6.

[0031] C_(graft) is the reaction product of ammonia and a cycliccarbonate functional group and has at least one structure selected fromthe group consisting of of formulas (I), (II) and (III):

[0032] wherein C′ is a saturated carbon having substituents selectedfrom hydrogen and alkyl groups of from one to six carbons, R is hydrogenor an alkyl group of from one to six carbons, and c_(ii) is a graftingmoiety selected from aliphatics, cycloaliphatics, polyurethane oligomersand polymers, nonionic groups, polyalkyldienes, triazines, hinderedamine light stabilizers, aromatic groups, ionic groups, and mixturesthereof.

[0033] k is from 1 to 95% by weight of the total sum of k, l, and m. l,is from 0 to 50% by weight of the total sum of k, l, and m, and m isfrom 1 to 95% by weight of the total sum of k, l, and m.

[0034] After this first multifunctional material is produced, the methodrequires that one or more different portions of the acrylic backbonepolymer (b) be subjected to successive or simultaneous reactions ofreaction (A) with different grafting materials (c) and reaction (B) withammonia, to make multiple multifunctional material of the formula:

[0035] wherein all variables are as defined above except that c_(ii) isdifferent for each additional multifunctional material.

[0036] The multifunctional materials made by the methods of theinvention are useful as a film-forming components in curablefilm-forming compositions, especially curable coating compositions,whether solventborne, liquid solvent free coatings, waterborne,electrodeposition, powder, or powder slurry. Automotive applicationsrequiring an optimum balance of finished film properties willparticularly benefit from the use of the primary carbamatemultifunctional materials made by the method of the invention. Finishedfilm-properties that improve with the use of the claimed multifunctionalmaterials include etch resistance, scratch and marring resistance, UVdurability, chip resistance, adhesion, and/or the like.

DETAILED DESCRIPTION OF THE INVENTION

[0037] The method of the invention requires the successive orsimultaneous reaction of a base material P with two different reactants,i.e., ammonia and a grafting material (c). Material P must comprise twoor more cyclic carbonate groups (bi) per molecule on average. Thus, atleast one cyclic carbonate group per molecule on average of material Pmust be reacted with ammonia, i.e., reaction (A). Reaction (A) willproduce a β or higher hydroxy primary carbamate functional group. Atleast one other cyclic carbonate group per molecule of material P onaverage must be reacted with a grafting material (c), i.e., reaction (B)to provide a hydroxy functional urethanized graft moiety.

[0038] Reactions (A) and (B) may occur in succession relative to oneanother and independent of order. That is, reaction (A) may begin and goto completion prior to the initiation of reaction (B). Alternatively,reaction (B) may begin and go to completion prior to the initiation ofreaction (A). In another embodiment, the two reactions may proceed andfinish simultaneously. Finally, a mixture of these various reactionschedules may be used, i.e., one or the other of the two reactions maybe begin prior to the other, with the other starting at some point priorto the completion of the first initiated reaction.

[0039] However, as used herein, the phrase “goes to completion” refersonly to the reaction of that amount of cyclic carbonate groups intendedfor conversion by particular reaction (A) or (B). At a minimum, however,at least one cyclic carbonate group per molecule, on average, is reactedwith each of reaction (A) and reaction (B). Thus, it is an aspect of theinvention that even if either reaction (A) or (B) goes to completionprior to the initiation of the other reaction, there will always be atleast one remaining cyclic carbonate group available for reaction in thesecond occuring reaction. That is, the method of the invention requiresthat both reaction (A) and (B) occur with one or more of the cycliccarbonate groups of material P on average per molecule. It is also anaspect of the invention that, when desired, there may be cycliccarbonate groups (bi) attached to material P that remain unreacted afterthe completion of reactions (A) and (B).

[0040] Suitable materials P are those materials that comprise two ormore cyclic carbonate groups (bi) and are of the formula:

[0041] wherein q is a number from 2 to 50 and n is a number from 0 to 6,preferably from 0 to 1. Thus, illustrative cyclic carbonate groups (bi)are those cyclic carbonate groups having various ring sizes as are knownin the art, such as five-membered cyclic carbonate rings, six-memberedcyclic carbonate rings, seven-membered cyclic carbonate rings, or fusedring systems containing the characteristic —O—CO—O— carbonate moiety.5-membered and 6 membered cyclic carbonate rings are preferred for useas cyclic carbonate groups (bi), with 5-membered rings being mostpreferred due to their commercial availability. Also, it will beappreciated that the carbons in the above cyclic carbonate structure arefully saturated with either hydrogen atoms or alkyl groups of from oneto six carbons.

[0042] Material P must have at least two cyclic carbonate groups,preferably more than two, and most preferably at least 3 cycliccarbonate groups on average per molecule of material P. Thus, while itis conceivable that there may be individual molecules that contain lessthan two cyclic carbonate groups, on average, each molecule will havetwo or more. In one preferred embodiment, material P will have from 3 to50 cyclic carbonate groups, more preferably from 3 to 20, and mostpreferably from 3 to 10 cyclic carbonate groups, on average per moleculeof material P.

[0043] In general, material P is a hydrocarbon-based material that mayor may not contain heteroatoms in those portions of material P notincluding cyclic carbonate group (bi) and any optional functionalgroups. Material P may be a compound, oligomer, polymer, or a mixturethereof. Material P may be aliphatic, cycloaliphatic, aromatic,unsaturated, saturated, and mixtures thereof and may have a numberaverage molecular weight of from 174 to 1,000,000 Daltons. Morepreferably, material P having at least two cyclic carbonate groups willhave a number average molecular weight of from 174 to 50,000 Daltons,most preferably from 188 to 8,000 Daltons. Preferred materials P willnormally contain heteratoms. “Heteroatoms” as used herein refers toatoms other than carbon or hydrogen. Preferred heteroatoms are O, N, Si,and mixtures thereof.

[0044] For the purposes of the instant invention, the term “oligomer”refers to materials having from two to nine repeating units or mixturesof repeating units. In general, suitable oligomers for use in theinstant invention will have number average molecular weights in therange of from 202 to 1499 Daltons.

[0045] “Polymer” as used herein refers to materials having at least tenrepeating units, more preferably greater than 10 repeating units. Ingeneral, polymers suitable for use as material P will have a numberaverage molecular weight in the range of from 1500 to 1,000,000 Daltons,preferably between 1500 and 50,000 Daltons, most preferably between 1500and 15,000 Daltons.

[0046] It will be appreciated by those of skill in the art that becauseoligomers and polymers are both based on repeating units of monomericmaterials; high molecular weight oligomers may overlap the low molecularweight end range for polymers.

[0047] “Compounds” as used herein refers to materials that do notcontain two or more of the same repeating units. In general, compoundshaving two or more cyclic carbonate groups will have number averagemolecular weights in the range of from 174 to 2000.

[0048] The term “repeating units” as defined as herein refers to groupsof atoms that are the reaction product result or residue of the reactionof two or more monomers. Such repeating units will generally have anindividual number average molecular weight in the range of from 28 to750 Daltons.

[0049] While material P may be a compound, an oligomer, a polymer or amixture thereof, material P will most preferably be a polymer and/oroligomer.

[0050] In addition to the required cyclic carbonate functional groups(bi), material P may optionally comprise one or more additionalfunctional groups (bii), different from required cyclic carbonatefunctional group (bi). In general, optional functional group (bii) maybe defined as any reactive functional group that is essentially inertwith respect to cyclic carbonate groups (bi) under the reactionconditions A and B. More preferably, optional functional group (bii)will also be reactive with a reactive functional group of a curing agent(B). In most cases, it is preferred that functional groups (bii) also beinert with respect to grafting material (c), including (ci), (cii), andany functional groups (cii_(fg)); and/or ammonia, under the reactionconditions A and B. Illustrative examples of optional functional groups(bii) include blocked isocyanates, hydroxy, aminoplast, ethylenicallyunsaturated groups, primary carbamate, and the like.

[0051] Examples of suitable oligomers and/or polymers useful as materialP include the following: biurets and isocyanurates, homopolymers ofdiisocyanate materials such as isocyanurates, acrylic, modified acrylic,polyurethane, polyester, polylactones, polyurea, alkyd, polysiloxane,polyethers, epoxy upgrades, mixtures thereof, and the like. Oligomersand polymers preferred for use as material P are polyurethane,polyester, acrylic, and the like. Most preferred polymers and oligomersfor use as material P are polyurethanes, acrylics and isocyanurates.

[0052] In one embodiment of the invention, the material P may be anacrylic. The acrylic polymer preferably has a molecular weight of 1500to 1,000,000, and more preferably of 1500 to 50,000. As used herein,“molecular weight” refers to number average molecular weight, which maybe determined by the GPC method using a polystyrene standard. Suchpolymers are well-known in the art, and can be prepared from monomerssuch as methyl acrylate, acrylic acid, methacrylic acid, methylmethacrylate, butyl methacrylate, cyclohexyl methacrylate, styrene,maleic anhydride, and the like as discussed below.

[0053] The required two or more cyclic carbonate functional groups (bi)can be incorporated into the ester portion of the acrylic monomer.

[0054] For example, in one preferred embodiment of the invention, thebase material P may result from the use of a monomer mixture (a) that ispolymerized under polymerization conditions, especially free radicalpolymerization conditions, to make an acrylic oligomer or polymerbackbone (b).

[0055] Monomer mixture (a) is comprised of ethylenically unsaturatedmonomers having at least one carbon-carbon double bond that is reactivewith another carbon-carbon double bond under conventional or controlledpolymerization conditions. As used herein, ‘polymerization’ refers tooligomerization or polymerization reaction conditions wherein thetemperature is between room temperature (approximately 20° C./68° F.)and no more than 180° C./356° F., more preferably from 70 to 140° C./158to 284° F., and most preferably from 110 to 140° C./230 to 284° F. Suchreaction conditions may relate to conventional polymerization reactionssuch as free radical polymerization as well as controlled or livingpolymerization reactions such as ATRP, and the like as discussed below.

[0056] In a preferred embodiment of the invention, polymerization asused herein refers to reaction conditions that are free of any catalyststhat can activate an oxirane group. Illustrative examples of suchoxirane activating catalysts are tertiary amine or quaternary salts(e.g., tetramethyl ammonium bromide), combinations of complex organotinhalides and alkyl phosphonium halides (e.g., (CH₃)₃SnI, Bu₄SnI, Bu₄PI,and (CH₃)₄PI), potassium salts (e.g., K₂CO₃, KI) in combination withcrown ethers, tin octoate, calcium octoate, and the like.

[0057] The most preferred polymerization techniques are free radicalpolymerizations that may take place in solvent or water but will mostpreferably take place in solvent. Illustrative examples of suitableorganic solvents include aromatic solvents, ketone solvents, estersolvents, ether solvents, alcoholic solvents, and combinations thereof.In a preferred embodiment of the invention, free radical polymerizationreaction conditions will be used which are free of catalysts such asLewis acids and strong sulphonic acids having a pK_(a) of less than 2.0.

[0058] In a most preferred embodiment, free radical polymerization ofethylenically unsaturated monomers will take place in the presence oftemperatures of from 80 to 140° C. an absence of any epoxy ringactivating catalysts, and an absence of any water or alcohols that arereactive with cyclic carbonate functional groups under suchtemperatures. In a most preferred embodiment, the oligomerization orpolymerization conditions will be such that at least two cycliccarbonate functional groups per molecule on average remain inert,preferably at least three or more cyclic carbonate functional groups onaverage per molecule, and most preferably from 3 to 50 cyclic carbonategroups on average per molecule.

[0059] Alternatively, the monomer mixture comprising the primarycarbamate functional ethylenically unsaturated monomer of the inventionmay be polymerized using controlled or living radical polymerizationprocesses as described by Matyjaszewski and Krysztof in Chem. Reviews,Vol. 101 pg 2921-2990 (2001), or by iniferter process as described byKuchanov, in J. of Polymer Science, Part A: Polymer Chemistry Vol 32 pg1557-1568 (1994), and Gaofenzi Xuebao Vol 2 pg 127-136 (2002),nitroxide-mediated polymerization as described by Zaremski, in RussianPolymer News Vol 4 pg 17-21 (1999), and Wang, in Abstracts of Papers,224th ACS National Meeting, Boston, Mass., United States, Aug. 18-22,2002 (2002), all of which are incorporated by reference herein.

[0060] It is an aspect of this embodiment of the invention that monomermixture (a) comprise a monomer (ai) having at least one cyclic carbonategroup and the structure:

[0061] wherein L is a linking group selected from aliphatic groups,cycloaliphatic groups, aromatic groups and mixtures thereof of from oneto seven carbons, n is a number from zero to six, preferably zero toone, and R is either hydrogen or an alkyl group of from one to sixcarbons.

[0062] L may contain heteratoms such O, N, S, and mixtures thereofand/or functional groups such as esters, ethers, urethanes, ureas,amides, and mixtures thereof. Preferred groups suitable for use aslinking group L are esters and urethanes, with esters being mostpreferred.

[0063] Monomer (ai) will be present in monomer mixture (a) in an amountof from 1 to 100% by weight, based on the total weight of monomermixture (a), more preferably from 5 to 90%, and most preferably from 20to 70%, based on the total weight of monomer mixture (a). Those skilledin the art will appreciate that the requirement that material P containon average at least two cyclic carbonate groups per molecular willnecessitate the use of higher number average molecular weights for thoseoligomers and/or polymers of material P made from monomer mixtureshaving a low weight percent of monomer (ai).

[0064] Monomer (ai) can be prepared by the reaction of a glycidyl-groupcontaining polymerization monomer with carbon dioxide to convert theoxirane group to a cyclic carbonate group. Examples of suitable oxiranegroup-containing polymerizable monomers include, without limitation,glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, and allylglycidyl ether. This can be done at any pressure from atmospheric up tosupercritical CO₂ pressures, but is preferably under elevated pressure(e.g., 60-150 psi). The temperature for this reaction is preferably60-150° C. Useful catalysts that activate the oxirane ring may be used.Illustrative catalysts include any that activate an oxirane ring, suchas tertiary amine or quaternary salts (e.g., tetramethyl ammoniumbromide), combinations of complex organotin halides and alkylphosphonium halides (e.g., (CH₃)₃SnI, Bu₄SnI, Bu₄PI, and (CH₃)₄PI),potassium salts (e.g., K₂CO₃, KI) preferably in combination with crownethers, tin octoate, calcium octoate, and the like.

[0065] Alternatively, cyclic carbonate functional ethylenicallyunsaturated monomers may be prepared by the reaction of ethylenicallyunsaturated monomers containing 1,2- or 1,3-diols with phosgene,dialkylcarbonates, or cyclic carbonates.

[0066] Finally, although not preferred, cyclic carbonate functionalethylenically unsaturated monomers can be prepared by the thermaldecomposition of ethylenically unsaturated monomers containingbeta-hydroxy primary carbamates.

[0067] Monomer mixture (a) may further optionally comprise one or moreadditional ethylenically unsaturated monomers (aii) that are differentfrom monomer (ai) and have one or more functional groups that areunreactive with the cyclic carbonate functional groups of monomer (ai)under oligomerization or polymerization conditions. That is, under freeradical polymerization conditions as defined above, the functionalgroups of monomers (aii) will not react with the cyclic carbonate groupof monomer (ai). In a most preferred embodiment, monomer mixture (a)will comprise one or more monomers (aii).

[0068] Monomer (aii) will be present in monomer mixture (a) in an amountof from 0 to 99% by weight, based on the total weight of monomer mixture(a), more preferably from 30 to 95% by weight, and most preferably from50 to 90% by weight, based on the total weight of monomer mixture (a).

[0069] Illustrative examples of such monomers (aii) include hydroxylfunctional ethylenically unsaturated monomers, isocyanate functionalethylenically unsaturated monomers, carboxylic acid functionalethylenically unsaturated monomers, urea functional ethylenicallyunsaturated monomers, carbamate functional ethylenically unsaturatedmonomers and mixtures thereof, wherein ethylenically unsaturatedmonomers are as defined above. Preferred monomers (aii) are hydroxylfunctional, acid functional, alkyl substituted, aryl substituted andisocyanate functional ethylenically unsaturated monomers

[0070] Illustrative hydroxyl functional ethylenically unsaturatedmonomers (aii) are hydroxyalkyl esters of acrylic acid or methacrylicacid such as hydroxyethylmethacrylate, hydroxypropylmethacrylate andmixtures thereof, with hydroxyethylmethacrylate being most preferred.

[0071] Illustrative isocyanate functional ethylenically unsaturatedmonomers (aii) include meta-isopropenyl-alpha,alpha-dimethylbenzylisocyanate and isocyanatoethyl methacrylate.Meta-isopropenyl-alpha,alpha-dimethylbenzyl isocyanate is mostpreferred.

[0072] Illustrative carboxylic acid functional ethylenically unsaturatedmonomers (aii) are acrylic acid, methacrylic acid and mixtures thereof,with methacrylic acid being preferred.

[0073] Suitable urea functional ethylenically unsaturated monomers (aii)include allyl urea.

[0074] Ethylenically unsaturated monomers having carbamate functionalityin the ester portion of the monomer may also be used as monomer (aii).Such monomers are well known in the art and are described, for example,in U.S. Pat. Nos. 3,479,328, 3,674,838, 4,126,747, 4,279,833, and4,340,497, the disclosures of which are hereby incorporated byreference. For example, one method of synthesis involves reaction of ahydroxy ester with urea to form the carbamyloxy carboxylate (i.e.,carbamate modified acrylate). Another method of synthesis reacts analpha, beta-unsaturated acid ester with a hydroxy carbamate ester toform the carbamyloxy carboxylate. Additionally, the hydroxy group on ahydroxyalkyl carbamate can be esterified by reaction with acrylic ormethacrylic acid to form a carbamate functional ethylenicallyunsaturated monomer. Other methods of preparing carbamate modifiedacrylic monomers are described in the art and can be utilized as well.

[0075] Monomer mixture (a) may further optionally comprise one or morenonfunctional ethylenically unsaturated monomers (aiii). Illustrativenonfunctional monomers (aiii) include vinyl monomers such as styrene,alpha-methyl styrene, vinyl toluene, tert-butyl styrene, and 2-vinylpyrrolidone and alkyl esters of acrylic acid and/or methacrylic acid.Illustrative examples of alkyl esters of acrylic acid and/or methacrylicacid include ethyl (meth)acrylate, butyl (meth)acrylate,2-ethylhexyl(meth)acrylate, cyclohexyl (meth)acrylate, lauryl(meth)acrylate, isodecyl (meth)acrylate, methyl (meth)acrylate.

[0076] Monomer (aiii) will be present in monomer mixture (a) in anamount of from 0 to 99% by weight, based on the total weight of monomermixture (a), more preferably from 30 to 95, and most preferably from 50to 90, based on the total weight of monomer mixture (a).

[0077] Monomer mixture (a) will be polymerized under free radical orcontrolled polymerization conditions to provide an acrylic backbonepolymer (b) having two or more cyclic carbonate functional groups (bi).Most preferably, free radical polymerization processes will be used.Acrylic backbone polymer (b) may also comprise optional functionalgroups (bii) if monomer mixture (a) comprised optional monomers (aii).

[0078] Modified acrylics having the required two or more cycliccarbonate functional groups (bi) can also be used as the material Paccording to the invention. Such acrylics may be polyester-modifiedacrylics or polyurethane-modified acrylics, as is well known in the art.Polyester-modified acrylics modified with ε-caprolactone are describedin U.S. Pat. No. 4,546,046 of Etzell et al, the disclosure of which isincorporated herein by reference. Polyurethane-modified acrylics arealso well known in the art. They are described, for example, in U.S.Pat. No. 4,584,354, the disclosure of which is incorporated herein byreference. A non-limiting example of one such polymer is an acrylicresin made up of hydroxyethyl methacrylate, methyl methacrylate, andbutyl acrylate which is then half capped with a diisocyanate such asisophorone diisocyanate to make an isocyanate functional polymer usefulas material P. Cyclic carbonate groups may be incorporated into suchmodified acrylics via the reaction of oxirane groups and CO₂ to formcyclic carbonate groups as discussed above. Examples of suitable oxiranegroup-containing polymerizable monomers include, without limitation,glycidyl acrylate, glycidyl methacrylate, glycidyl crotonate, and allylglycidyl ether.

[0079] Polyesters and ester oligomers having cyclic carbonate functionalgroups (bi) can also be used as the material P in the method of theinvention. Such polyesters are well-known in the art, and may beprepared by the polyesterification of organic polycarboxylic acids(e.g., phthalic acid, hexahydrophthalic acid, adipic acid, maleic acid)or their anhydrides with organic polyols containing primary or secondaryhydroxyl groups (e.g., ethylene glycol, butylene glycol, 1,6-hexanediol,neopentyl glycol).

[0080] Cyclic carbonate groups may be incorporated into polyesters asfollows. Polyesters, formed as described above, will generally haveeither hydroxy, acid or a mixture of both functionalities. Suchfunctionalities can be used to provide the required cyclic carbonategroups (bi). For example, a hydroxy functional polyester may be reactedwith a diisocyanate to form an isocyanate functional polyester. Thereaction of this material with glycidol will form an epoxy functionalpolyester with internal urethane links with can then be reacted with CO₂to form cyclic carbonate groups. Polyesters that contain 1,2 or1,3-diols can be converted into cyclic carbonate groups by reaction withcarbonates such as dimethyl carbonate or diphenyl carbonate or byreaction with cyclic carbonates such as ethylene or propylene carbonateor by reaction with phosgene. Cyclic carbonate groups can also beincorporated by the reaction of acid or hydroxy groups on the polyesterwith respectively, allyl alcohol or vinyl acetic acid, followed byreaction with peroxide and then carbon dioxide.

[0081] Other functional polyesters can be formed though the use ofspecialty capping alcohols and acids that are added during the polyesterformation. For example, the addition of a hydroxy alkene followed byreaction with hydrogen peroxide will result in the placement of an epoxygroup on the polyester. Reaction of this epoxy polyester with carbondioxide will also result in the formation of a cyclic carbonatefunctional polyester.

[0082] Polyurethanes and urethane oligomers having required cycliccarbonate functional groups (bi) are also known in the art. They can beprepared by a chain extension reaction of a polyisocyanate (e.g.,hexamethylene diisocyanate, isophorone diisocyanate, MDI, etc.) and apolyol (e.g., 1,6-hexanediol, 1,4-butanediol, neopentyl glycol,trimethylol propane). Formulating with an appropriate amount of excesspolyisocyanate will result in the polyurethane having free isocyanatefunctionality. Use of glycidol or 3-hydroxypropylene carbonate, forexample, will functionalize the polyurethane with epoxy or cycliccarbonate groups respectively. As described above, epoxy groups can beconverted into cyclic carbonate groups via reaction with CO₂.

[0083] Compounds suitable for use as material P include mono orpolyfunctional compounds such as nonchain-extended aliphatics,cycloaliphatics, aromatics which may or may not contain heteroatoms andwhich contain two or more cyclic carbonate groups (bi) or functionalgroups which may be converted into cyclic carbonate groups.

[0084] Examples of compounds suitable for use as material P includesimple aliphatic functional materials such as erythritol bis-carbonate,monomeric diisocyanates like hexane diisocyanate, aliphatic polyaminessuch as 1,6-hexane diamine, anhydrides such as succinic anhydride,polyacids such as dodecane dioic acid, compounds having mixedfunctionality such as hydroxy pivalic acid, the like, and mixturesthereof. Aromatic functional materials may also be used such as2,2-bis(4-hydroxyphenyl)propane. Suitable heteroatom functionalmaterials include hydroxyneopentyl hydroxy pivalate. It will beappreciated that such compounds that do not have two or more cycliccarbonates thereon do contain functional groups that can be convertedinto the required two or more cyclic carbonate groups as describedherein.

[0085] Other examples of suitable oligomers for use as material Pinclude heterocyclic materials based on triazines and isocyanurates suchas triamino triazine and tris-glycidyl isocyanurate.

[0086] Most preferred for use as material P herein are acrylic oligomersand polymers made using the (meth)acrylate esters of glycerine carbonateor 4-hydroxymethyl-1,3-dioxan-2-one, urethanes and acrylicsfunctionalized using hydroxy cyclic carbonates such as glycerinecarbonate, and isocyanurate based oligomers such as1,3,5-triazine-2,4,6(1H,3H,5H)-trione.

[0087] On the average, at least one cyclic carbonate group (bi) of anymaterial P must undergo reaction (A) with ammonia to produce a reactionproduct comprising material P having at least one β or higher hydroxyprimary carbamate group.

[0088] It will be appreciated that the phrase “β or higher hydroxyprimary carbamate group” refers to functional groups of the structure:

[0089] wherein C′ is a saturated carbon having substituents selectedfrom hydrogen and alkyl groups of from one to six carbons, and n is anumber from 0 to 6, preferably from 0 to 4, and most preferably from 0to 1. The term “β” or “beta” refers to the structure above when n is 0.Similarly, gamma refers to the above structure when n is 1. The value ofn will be dependent upon the number of carbons in the cyclic carbonatefunctional group (bi).

[0090] The reaction (A) with ammonia will generally take place undermild conditions at temperatures from 0 to 60° C. It can be carried outin organic solvents such as methanol, or the reaction can be carried inwater, or a mixture of water and organic solvents. When water is used asthe sole solvent or as a part of a solvent blend, ammonium hydroxide maybe used in place of ammonia. Alternatively, liquefied ammonia may beused as the solvent. However, it will be appreciated that the reactionwith the grafting material (c) must occur first when ammonia is used asthe solvent, or an excess of ammonia is used.

[0091] It will be appreciated that when the reaction with ammonia occursbefore or at the same time as the reaction with the grafting material(c), great care must be used in measuring the molar amount of ammoniaused to ensure that cyclic carbonate functional groups remain forreaction with grafting material (c). Under these conditions, it ispreferred that solutions of ammonia in water (ammonium hydroxide) orsolvent be used to facilitate greater control of the concentration ofammonia as compared to that achievable with ammonia gas.

[0092] Finally, the amount of ammonia used will be dependent upon thedesired number of β and higher hydroxy primary carbamate groups presenton average per molecule of final reaction product.

[0093] The method of the invention also comprises the reaction (B) ofmaterial P with at least one grafting material (c).

[0094] Grafting material (c) will be at least one material comprising atleast one amine group (ci) and at least one grafting moiety (cii).Grafting material (c) may be monomeric, oligomeric, or polymeric innature.

[0095] The at least one amine group (ci) of grafting material (c) willbe at least one amine group that is selected from primary amines,secondary amines, and mixtures thereof. Primary amines are mostpreferred for use as the at least one amine group (ci).

[0096] That portion of grafting material (c) which is not amine group(ci) may be referred to as graft moiety (cii) and may be a material,oligomer, or polymeric in nature. Grafting moiety (cii) will generallycomprise a backbone which may be aliphatic, cycloaliphatic, aromatic,unsaturated and mixtures thereof. Grafting moiety (cii) may also containhetroatoms such as O, S, N, Si, and the like. Grafting moiety (cii) canalso possess additional functional groups (cii_(fg)) that are notreactive towards a cyclic carbonate group under the reaction conditionsA or B.

[0097] The selection of graft moiety (cii) is dependent upon the desiredperformance properties of the final multifunctional material of theinvention. Graft moiety (cii) can be selected to provide particularproperties or attributes. For example, graft moiety (cii) can beselected to provide flexibility via the introduction of long chain fattyacids. Alternatively, as discussed below, graft moiety (cii) can beselected to impart or control water dispersibility or solubility.

[0098] Illustrative graft moieties (cii) are aliphatics;cycloaliphatics; polyurethane oligomers and polymers; nonionic groupssuch as ether groups, polyether groups, polyoxyalkylene groups,halogen-containing groups, ester groups, polyester groups, polylactonesgroups; polyalkyldienes; triazines; hindered amine light stabilizers(HALS); aromatic groups; and ionic groups such as secondary amines,tertiary amines, acid groups, salted acid groups, and mixtures thereof.Most preferred graft moieties (cii) will be selected from the group ofionic groups such as acid, salted acid groups, and mixtures thereof.

[0099] Any suitable graft moiety (cii) may also contain functionalgroups (cii_(fg)) that are essentially inert with respect to cycliccarbonate groups, functional groups (bii), ammonia, and/or amine groupsunder the reaction conditions A and B. Illustrative examples offunctional groups (cii_(fg)) include blocked isocyanates, hydroxy, acid,carbamate, ethers, polyethers, esters, polyesters, amines not reactablewith cyclic carbonates, aminoplast, ethylenically unsaturated groups andthe like.

[0100] In a most preferred embodiment, grafting material (c) willcomprise such functional groups (cii_(fg)). Most preferred functionalgroups (cii_(fg)) are hydroxy, acid, carbamate, ethers, and polyethers.

[0101] Preferred for use as graft material (c) when making the β orhigher hydroxy primary carbamate multifunctional materials of theinvention are hydroxyamines such as hydroxypropyl amine, amino primarycarbamates such as 3-aminopropyl carbamate, ethylenically unsaturatedamines such as allylamine, halogen containing amines such as polychlorohexyl amine, nonionic amines such as amino functionalizedpolyethyleneoxide and aminocrotonylnitrile, silane functional aminessuch as aminopropyl trimethylsilane, amino acids such as 4-aminobutyricacid, and mixtures thereof. Most preferred for use as grafting material(c) are hydroxy amines, carbamate amines, amino acids, and unsaturatedamines.

[0102] In a most preferred embodiment, if the at least one amine group(ci) is a primary amine, grafting moiety (cii) must have six or morecarbons or have at least one additional functional group (cii_(fg)) suchthose discussed above.

[0103] In a special case, the functional group (cii_(fg)) may be able toform a reversible salt with another functional group in the reactionmixture as long as it does not prevent the desired reactions fromoccuring. Thus, primary or secondary amino acids, for example, which canform a reversible salt with themselves can be used.

[0104] In another preferred embodiment, the desired β or higher hydroxyprimary carbamate multifunctional materials produced by the method ofthe invention will be waterborne materials. “Waterborne” as used hereinrefers to materials that are either water-soluble or water dispersible.A “water soluble” graft material refers to a material that is capable tomixing with water to form a homogenous mixture. A “water dispersible”graft material refers to a material that upon mixing with water forms amicroscopically heterogeneous mixture of two or more finely dividedphases.

[0105] To provide waterborne materials of the invention, graft moiety(cii) must be selected from the group consisting of secondary amines,tertiary amines, acid groups, salted acid groups, nonionic groups,nitrites, polyethers, polyesters, amides, ureas, and mixtures thereof,preferably from the group consisting of acid groups, salted acid groups,nonionic groups, nitrites, polyethers, amides, ureas, and mixturesthereof, and most preferably from the group consisting of acids.

[0106] However, if a multifunctional waterborne material of theinvention is desired, and graft moiety (cii) comprises an ionic groupsuch as salted acid groups, graft moiety (cii) will preferably have fromone to no more than five carbons for each ionic group, preferably fromone to four carbon atoms for each ionic group. If a multifunctionalwaterborne material of the invention is desired and the graft moiety(cii) is nonionic, graft moiety (cii) should comprise from one to nomore than three carbons for each additional nonionic functional group(cii_(fg)).

[0107] In a most preferred embodiment of the method of the inventionused to make waterborne β or higher hydroxy primary carbamatemultifunctional materials, certain relationships between the selectionof the amine group (ci) and grafting moiety (cii) will be observed. Whenthe grafting moiety (cii) is a secondary amine, the amine group (ci)will be a primary amine. When the grafting moiety (cii) is a tertiaryamine, the amine group (ci) will be either a primary amine or secondaryamine. If the grafting moiety (cii) is an acid, salted acid, ornonionic, the amine group (ci) will be either a primary amine orsecondary amine.

[0108] Thus, certain grafting materials (c) are preferred when makingwaterborne β or higher hydroxy primary carbamate multifunctionalmaterials of the invention. For example, illustrative examples ofpolyamines suitable for use as graft material (c) in this embodimentinclude dimethylamino butylamine. Suitable amino acids useful as graftmaterial (c) include aminobutyric acid, and the salted versions thereof.Salted forms of suitable acid groups may be obtained via reaction withammonia or amines such as triethyl amine. Illustrative examples of graftmaterials (c) containing nonionic groups include amine functionalizedpolyethylene oxides and propylene oxides, and nitriles such asaminocrotonylnitrile.

[0109] Grafting material (c) will be provided in the method of theinvention in an amount sufficient to react with from 1 to 99% of thetotal number of cyclic carbonate functional groups (bi), more preferablyfrom 5 to 90% and most preferably from 5 to 20% of the total number ofcyclic carbonate functional groups (bi). The minimum and maximum percentlisted above is dependant on the number average molecular weight of thematerial P in order to maintain the requirement that the finalmultifunctional material contains at least one beta or higher hydroxyprimary carbamate group and at least one graft moiety (cii).

[0110] It will be appreciated that additional grafting material (c) maybe added based on other functional groups (bii) present on any materialP in those cases wherein functional groups (bii) are not inert withrespect to grafting material (c). For example, grafting material (c) maybe used to react with acid groups to provide water dispersible ionicgroups.

[0111] An additional reaction (C) may optionally be added to the methodof the invention used to make waterborne β or higher hydroxy primarycarbamate multifunctional materials. Reaction (C) may be used to saltany saltable moieties present in grafting moiety (cii) to provide waterdispersible groups. One or more salting agents (f) may be reacted withany grafting moiety (cii) that are saltable to make a salted site(cii*). Examples of saltable grafting moieties (cii) are secondaryamines, tertiary amines, acid groups, and mixtures thereof Illustrativesalting agents (f) include organic acids such as lactic acid and acidicacid, organic bases such as triethyl amine and aminopropanol, inorganicacids based on halides, phosphorous and sulfur and bases such as metalhydroxides. It will be appreciated that salting agents (f) may be usedin any desired amount to obtain the desired level of waterdispersibility.

[0112] Depending upon the selection of grafting moiety (cii), reaction(C) may be required to obtain a waterborne β or higher hydroxy primarycarbamate multifunctional materials of the invention. In general, if awaterborne final product is desired, when (i) the at least one graftingmoiety (cii) is a secondary amine or a tertiary amine, or (ii) the atleast one grafting moiety (cii) is an acid group and the reaction ofmaterial P with ammonia proceeds before the reaction of material P withgrafting material (c), the method of the invention will require furtherreacting the grafting moiety (cii) with one or more salting agents (f)to provide a salted site (cii*).

[0113] If material P is an acrylic and the grafting material (c) is notprovided during the free radical polymerization of a monomer mixture(a), grafting material (c) will be reacted with acrylic backbone polymer(b) under reaction conditions sufficient to react the amine group (ci)of grafting material (c) with the cyclic carbonate functional group (bi)of acrylic backbone polymer (b).

[0114] Illustrative grafting reaction conditions are temperaturesbetween 0 to 140° C., more preferably between 0 and 120° C., and mostpreferably between 0 and 60° C.

[0115] In one embodiment of the invention, optional functional groups(bii) of acrylic backbone polymer (b) may be reacted with one or moreoptional compounds (d) to provide a functional group (bii′). Thereaction between functional groups (bii) and optional compound (d) mayoccur before, during or after the reaction of grafting material (c) andmaterial P. Most preferably, if optional functional groups (bii) areused as a precursor to desired functional group (bii′), such reactionsmay occur before or after reactions A and B, most preferably after thecompletion of reactions A and B. Functional group (bii) may thus act asa secondary-grafting site or as a precursor to a different functionalgroup that was difficult to incorporate earlier. For example, a materialP containing acid functional groups (bii) may be salted with a tertiaryamine before the initiation of reaction A or B.

[0116] Compound (d) may be monomeric, oligomeric, or polymeric innature, with monomeric being most preferred. It will be appreciated thatcompound (d) must have at least one functional group reactive withoptional functional group (bii). The selection of compound (d) will bedependent upon the identity of both functional groups (bii) and (bii′).Illustrative compounds include those discussed below with respect tocompounds (e).

[0117] It will be appreciated that the reaction of the at least oneamine group (ci) of the grafting material (c) and the cyclic carbonategroup (bi) of the acrylic backbone polymer (b) results in the formationof a urethane group and a hydroxyl group beta or higher to the urethanegroup. The urethane group links the grafting moiety (cii) with theacrylic backbone polymer (b).

[0118] In another embodiment of the invention some, all, or none of thehydroxyl groups formed from either the reaction of the cyclic carbonatefunctional group (bi) and the amine group (ci) or ammonia may be reactedwith one or more compounds (e).

[0119] Compounds (e) may be monomeric, oligomeric, or polymeric innature. Suitable compounds (e) include those compounds that have atleast one functional group reactive with hydroxyl. In anotherembodiment, the one or more compounds (e) may comprise compounds orgroups such as those described above in regards to grafting moiety(cii). It will therefore be appreciated that the hydroxyl group may actas a secondary-grafting site. Alternatively, the hydroxyl group may beconverted into a different functional group that could not easily beintroduced previously. For example, the hydroxyl group may be reactedwith a mono- or polyisocyanate compound to provide an isocyanatefunctional urethanized acrylic graft polymer. Alternatively, thehydroxyl group may be converted into an acid group by reaction with acyclic anhydride. Finally, the hydroxyl group may also be converted to acarbamate group by reaction with phosgene and ammonia.

[0120] Thus, additional multifunctionality may be incorporated into theurethanized graft materials of the invention via reaction of thehydroxyl groups resulting from said amine/cyclic carbonate reaction withcompounds (e) or by the use of optional functional groups (bii) or byreaction of functional groups (bii) with compounds (d).

[0121] The use of the method of the invention provides an improved wayto make multifunctional graft materials that were not previouslycommercially feasible to manufacture. For example, with the use of themethod of the invention, urethanized graft materials having blockedisocyanate or urethane containing groups and hydroxyl groups can beobtained.

[0122] As discussed previously, the method of the invention allows forthe simultaneous or successive reactions of reactions (A) and (B) withthe two or more cyclic carbonate functional groups (bi) of material P.

[0123] However, if material P is an acrylic, grafting material (c) andammonia may be provided during the polymerization of monomer mixture (a)or after, but will most preferably be provided after the acrylicbackbone (b) is obtained. If grafting material (c) or ammonia isprovided during the polymerization of monomer mixture (a) so thatgrafting occurs simultaneously with polymerization, grafting material(c) must be free of any carbon-carbon double bonds which couldpolymerize when subjected to polymerization conditions.

[0124] It will also be appreciated that the multifunctional materials ofthe invention can be designed to have a wide range of hydroxyl and/oracid values. The graft materials of the invention may be used insolventborne, solventless liquid, waterborne including electrodepositioncoatings, or powder coating compositions.

[0125] The method of the invention will generally provide β or higherhydroxy primary carbamate multifunctional materials of the formula:

(C_(graft))_(i)—P—(C_(NH3))_(j)

[0126] wherein P is a material, oligomer, or polymer as discussed above,C_(graft) is the reaction product of graft material c and a cycliccarbonate functional group (bii), C_(NH3) is the reaction product ofammonia with a cyclic carbonate functional group (bii), and i and jrepresent the total number of both functional groups.

[0127] P is defined as above except that in this formula, P may, but isnot required to, contain two or more cyclic carbonate groups (bi) butmay further comprise additional functional groups (bii) that are inertwith respect to cyclic carbonate functional groups under the reactionconditions of A and B.

[0128] C_(graft) is the reaction product of graft material c discussedabove and a cyclic carbonate functional group. C_(graft) will have astructure selected from the group of formulas (I), (II) and (III):

[0129] wherein C′ is a saturated carbon having substituents selectedfrom hydrogen and alkyl groups of from one to six carbons, R is hydrogenor an alkyl group of from one to six carbons, and c_(ii) is a graftingmoiety as described above.

[0130] i and j represent the total number of the respective functionalgroups and may be the same or different, but will most preferably bedifferent. i is a number from 1 to about 49, preferably from 1 to 20 andmost preferably from 1 to 10, while j is a number from 1 to about 49,preferably from 1 to 30 and most preferably from 1 to 10.

[0131] C_(NH3) is the reaction product of ammonia with a cycliccarbonate functional group and will have a structure selected from thegroup of formulas (I), (II) and (III):

[0132] wherein C′ is a saturated carbon having substituents selectedfrom hydrogen and alkyl groups of from one to six carbons, and n is anumber from 0 to 6, preferably from 0 to 4, and most preferably from 0to 1.

[0133] In a particularly preferred embodiment of the invention, P willbe an acrylic oligomer or polymer. In this embodiment, the β or higherhydroxy primary carbamate acrylic multifunctional materials of theinvention will have the formula:

[0134] wherein A is the residue resulting from the polymerization of anethylenically unsaturated monomer which does not contain a cycliccarbonate group but may contain a functional group (bii), L is a linkinggroup, p is number of from 0 to 5, C_(graft) is the reaction product ofgraft material c and a cyclic carbonate functional group as discussedabove, C_(NH3) is the reaction product of ammonia with a cycliccarbonate functional group as discussed above, and k, l, and m representthe total number of monomers or repeating units. It will be appreciatedthat in the above formula, the bond connecting L to the ethylenicallyunsaturated backbone is not attached to either carbon but is depicted assomewhere in the middle to illustrate the two possible isomers.

[0135] Ethylenically unsaturated monomers suitable for providingrepeating units A may be as described above with respect toethylenically unsaturated monomers (aii) and (aiii).

[0136] L is a linking group selected from aliphatic groups,cycloaliphatic groups, aromatic groups and mixtures thereof of from oneto seven carbons. L may contain heteratoms such O, N, S, and mixturesthereof and/or functional groups such as esters, ethers, urethanes,ureas, amides, and mixtures thereof. Preferred groups suitable for useas linking group L are esters and urethanes, with esters being mostpreferred.

[0137] p is number of from 0 to 5, with numbers of from 1 to 5 beingpreferred and 1 being most preferred. It will thus be appreciated that Lis an optional linking group but one which will preferably be present.

[0138] C_(graft) and C_(NH3) are as defined above.

[0139] k, l, and m represent the total number of monomers comprising thedesired β or higher hydroxy primary carbamate functional acrylic polymeror oligomer of the invention. k is from 1 to 95% of the total sum of k,l, and m, preferably from 5 to 80, and most preferably from 20 to 50,based on the total sum of k, l, and m. l is from 0 to 98% of the totalsum of k, l, and m, preferably from 30 to 95%, and most preferably from50 to 90%, based on the total sum of k, l, and m. m is from 1 to 95% ofthe total sum of k, l, and m, preferably from 5 to 80 and mostpreferably from 20 to 60, based on the total sum of k, l, and m

[0140] When the method of the invention is used to provide waterborne βor higher primary carbamate functional materials, the values of i and jin the formula:

(C_(graft))_(i)—P—(C_(NH3))_(j)

[0141] may be useful in predicting the degree of water solubility. Thatis, as noted above, materials useful in waterborne compositions mayrange from completely water soluable to those which are relativelyinsoluable but which are stabilized in water by the formation ofmicelles via dispersible functional groups. As noted above, i and jrepresent the total number of the respective functional groups.

[0142] Combined with number average molecular weight of P, the values ofi and j may be used as a guide to predict the water dispersibility orsolubility of the resulting β or higher hydroxy primary carbamatefunctional material. For example, when the result of dividing themolecular weight of material P by the sum of i+j is between 500 and2000, and when the result of dividing the molecular weight of material Pby just i is between 320 to 1000, the waterborne multifunctionalmaterials of the invention may be suitable for use in electrodepositioncoating compositions wherein the multifunctional material is initiallydispersible in waterborne but precipitates out upon the introduction ofan electrical current. Alternatively, when the result of dividing themolecular weight of material P by the some of i+j is between 400 and800, and the result of dividing the molecular weight of material P by iis between 450 to 1500, the waterborne multifunctional materials of theinvention may be described as suitable for use in aqueous dispersions.Finally, when the result of dividing the molecular weight of material Pby the sum of i+j is less than 600, and the result of dividing themolecular weight of material P by i is between 320 to 2500, thewaterborne multifunctional materials of the invention may be describedas materials which are substantially soluble in water. However, it willbe appreciated that the behavior of the multifunctional materials inwater is also dependent upon the nature of material P as well as thepolar/ionic nature of graft moiety (cii).

[0143] More precisely, it may be stated that the water dispersibilityand/or solubility of the waterborne multifunctional materials of theinvention may be identifiable based on two values calculated using i, j,and the number average molecular weight of P (P_(MW)), i.e., WV₁ and WV₂wherein

WV ₁ =P _(MW)÷(i+j) and WV ₂ =P _(MW)÷(i).

[0144] It may be generally stated that waterborne multifunctionalmaterial of the invention will be electrodepositable if WV₁ is a numberfrom 500 to 2000 and WV₂ is a number from 320 to 1000; water dispersibleif WV₁ is a number from 400 to 800 and WV₂ is a number from 450 to 1500;and water soluble if WV₁ is a number less than 600 and WV₂ is a numberfrom 320 to 2500.

[0145] It will be appreciated that the amounts of ammonia and differentgrafting materials (c) may be varied to selectively determine the waterdispersibility or solubility of waterborne materials by controlling theresult values of i and j as discussed above. The relative ratio of i andj needed to achieve a set level of water solubility is dependent on themake up of P, grafting material c and the overall molecular weight, andmust be determined on a case by case bases. However, the foregoingvalues are illustrative of preferred embodiments.

[0146] The method of the invention can be also used to provide animproved method of manufacturing a number of different multifunctionalacrylic oligomers or polymers. For example, a coating manufacturerproducing a large number of acrylic based products having differentfunctionalities can now produce a single large batch or “masterbatch” ofa cyclic carbonate functional acrylic oligomer or polymer. It will beappreciated that the production and storage of a large volume of asingle material increases efficiency and allows for economies of scale.Various acrylic based products having different functional groups canthen be obtained using the method of the invention.

[0147] For example, a first portion of the masterbatch of cycliccarbonate functional acrylic material may be reacted with ammonia and agrafting material (c) such as a fatty amine to provide a resin that isusable for solvent borne flexible clearcoats. A second portion of themasterbatch may be reacted with ammonia and a different graftingmaterial (c) such as a primary aminoacid that can be salted to provide awaterborne material useful in electrodeposition coating compositions. Athird portion of the masterbatch of cyclic carbonate functional acrylicmaterial may be reacted with sufficient amounts of ammonia and agrafting material (c) such as an amine functional polyethylene oxideoligomer to provide a 100% water soluble material useful in waterbornebasecoats. A fourth portion of the masterbatch may be reacted withsufficient amounts of ammonia and a grafting material (c) such as anamino functional polyurethane to provide a fil-forming binder suitablefor use in anti-chip coatings and primers.

[0148] The urethanized and β or higher hydroxyl primary carbamatemultifunctional materials of the invention are particularly suitable foruse in automotive coating compositions, especially electrodepositioncoatings, primers, topcoats, basecoats, and/or clearcoats, withclearcoats being especially preferred.

[0149] Coating compositions comprising the multifunctional materials ofthe present invention preferably form the outermost layer or layer ofcoating on a coated substrate. Preferably, the instant coatingcompositions are applied over one or more layers of primer coatings. Forexample, the coating compositions of the invention may be used as anautomotive topcoat coating applied over a layer of electrocoat primerand/or primer surfacer.

[0150] When such coating compositions are used as topcoat coatings, theypreferably have a 20 degree gloss, as defined by ASTM D523-89, of atleast 80 or a DOI, as defined by ASTM E430-91, of at least 80, or both.Such gloss and DOI are particularly useful in providing an automotivefinish that will appeal to the buyer of the vehicle. Topcoat coatingsmay be one coat pigmented coatings or may be a color-plus-clearcomposite coating.

[0151] Coating compositions comprising the multifunctional materials ofthe present invention, if used as a one coat pigmented coating or thecolor coating of a color-plus-clear composite coating, will include oneor more pigments well-known in the art, such as inorganic pigments liketitanium dioxide, carbon black, and iron oxide pigments, or organicpigments like azo reds, quinacridones, perylenes, copperphthalocyanines, carbazole violet, monoarylide and diarylide yellows,naphthol orange, and the like.

[0152] In a preferred embodiment, the coating composition of the presentinvention is the clearcoat of a color-plus-clear composite coating. Theclearcoat may be applied over a color coat according to the invention ormay, alternatively, be applied over a color coat of a formulationalready known in the art. Pigmented color coat or basecoat compositionsfor such composite coatings are well known in the art and do not requireexplanation in detail herein. Polymers known in the art to be useful inbasecoat compositions include acrylics, vinyls, polyurethanes,polycarbonates, polyesters, alkyds, and polysiloxanes. Such basecoatsmay comprise the acrylic graft copolymer of the invention. Preferredpolymers include acrylics and polyurethanes, especially themultifunctional materials of the invention. In one preferred embodimentof the invention, the basecoat composition also utilizes a β or higherhydroxy primary carbamate multifunctional material of the invention.

[0153] Curable coating compositions comprising the multifunctionalmaterials of the invention will be crosslinkable and will thus compriseone or more type of crosslinking agents having one or more crosslinkablefunctional groups. Such groups include, for example, hydroxy,isocyanate, amine, epoxy, acrylate, vinyl, silane, and acetoacetategroups. These groups may be masked or blocked in such a way so that theyare unblocked and available for the cross-linking reaction under thedesired curing conditions, generally elevated temperatures. Usefulcrosslinkable functional groups include hydroxy, epoxy, acid, anhydride,silane, and acetoacetate groups. Preferred crosslinking agents will havecrosslinkable functional groups that include hydroxy functional groupsand amino functional groups and isocyanate groups. Di- and/orpolyisocyanates and/or aminoplast resins are most preferred for use ascrosslinking agents in coating compositions comprising the acrylic graftpolymer of the invention. Other mixed crosslinkers may also be used.

[0154] For example, basecoat-coating compositions comprising themultifunctional materials of the invention may require two or moreseparate crosslinking agents in order to react with both the primarycarbamate group and the functional groups of the graft moiety (c). Forexample, the crosslinking agent may be an aminoplast resin, apolyisocyanate and blocked polyisocyanate resin (including anisocyanurate, biuret, or the reaction product of a diisocyanate and apolyol having less than twenty carbon atoms), and an acid or anhydridefunctional crosslinking agent.

[0155] Other materials well-known to the coatings artisan, for example,surfactants, fillers, stabilizers, wetting agents, dispersing agents,adhesion promoters, UV absorbers, light stabilizers such as HALS,antioxidants, solvents, catalysts, and/or rheology control agents, maybe incorporated into the coating composition. The amount of thesematerials used must be controlled to achieve the desired performanceproperties and/or to avoid adversely affecting the coatingcharacteristics.

[0156] It will be appreciated that suitable solvents include organicsolvents, water, water-soluble solvents, and mixtures thereof. It willbe appreciated that solvent borne coating may comprise minor amounts ofwater while waterborne coatings such as electrodeposition coatings maycomprise organic solvents.

[0157] Coating compositions can be coated onto an article by any of anumber of techniques well known in the art. These include, for example,spray coating, dip coating, roll coating, curtain coating, and the like.For automotive body panels, spray coating is preferred. When thecoatings will be relatively thick, they are usually applied in two ormore coats separated by a time sufficient to allow some of the waterand/or solvent evaporate from the applied coating layer (“flash”). Thecoats as applied are usually from 1 to 3 mils of the coatingcomposition, and a sufficient number of coats are applied to yield thedesired final coating thickness.

[0158] Where a color-plus-clear composite coating is applied to theprepared substrate, the color coat is usually applied in one or twocoats, allowed to flash, and the clear coat is then applied to theuncured color coat in one or two coats. The two coating layers are thencured simultaneously. Preferably, the cured base coat layer is 0.5 to1.5 mils thick and the cured clear coat layer is 1 to 3 mils, morepreferably 1.6 to 2.2 mils thick.

[0159] Coating compositions comprising the multifunctional materials ofthe invention are preferably subjected to conditions so as to cure thecoating layers. Although various methods of curing may be used, thermalcuring is preferred. Generally, thermal curing is effected by exposingthe coated article to elevated temperatures provided primarily byradiative heat sources. Curing temperatures will vary depending on theparticular blocking groups used in the crosslinking agents, however theygenerally range between 93 degree C. and 177 degree C. In a preferredembodiment, the cure temperature is between 135 degree C. and 165 degreeC. In another preferred embodiment, a blocked acid catalyst is includedin the composition and the cure temperature is between 115 degree C. and140 degree C. In a different preferred embodiment, an unblocked acidcatalyst is included in the composition and the cure temperature isbetween 80 degree C. and 100 degree C. The curing time will varydepending on the particular components used and physical parameters,such as the thickness of the layers. Typical curing times range from 15to 60 minutes, and preferably 15-25 minutes at the target temperature.

PROPHETIC EXAMPLES Example 1 Preparation of an Acrylic Backbone Polymer(P) According to the Invention

[0160] A solution of 25.58 parts of amyl acetate is heated under aninert atmosphere to reflux (˜144° C./291° F.). The inert air is thenturned off and a mixture of 49.0 parts of(2-Oxo-1,3-dioxolan-4-yl)methyl methacrylate, 6.1 parts of methylmethacrylate, 6.1 parts of butyl acrylate and 8.5 parts of a 50%solution of t-butylperacetate in odorless mineral spirits is added overthree hours while keeping the system at reflux. Then 4.72 parts of amylacetate is added. The final resin will have a NV of about 63.3%

Example 2 Preparation of an Acrylic Graft Beta or Greater HydroxyPrimary Carbamate Polymer According to the Invention for Use in PowderCoatings

[0161] To a stirred solution of 50 parts of the product from Example 1is added 29.3 parts of a 20% water solution of aminopropanol. Thereaction is followed by amine titration. When more than 95% of the amineis consumed, 20 parts of concentrated ammonium hydroxide solution isadded. The reaction is followed by infrared spectroscopy. Once all ofthe cyclic carbonate groups are consumed, the excess ammonia and solventare removed by vacuum distillation. The final 100% NV resin can be usedfor formulating powder coatings will have Mn of greater than 1700Daltons, a primary carbamate equivalent weight of about 605 g/equ, and ahydroxy equivalent weight of about 306 g/equ.

Example 3 Preparation of an Acrylic Graft Beta or Greater HydroxyCarbamate Polymer According to the Invention for Use inElectrodeposition Coatings

[0162] To a stirred solution of 50 parts of the product from example oneis added 2.1 parts of aminobutanoic acid and 50 parts of methanol. Thereaction mixture is then heated to 55° C. and followed by GC analysisOnce more than 95% of the amino acid is consumed, the reactiontemperature is cooled to 20° C. and ammonia gas is bubbled into thereaction mixture. The reaction is followed by infrared spectroscopy.Once all of the cyclic carbonate groups are consumed, the excess ammoniaand solvent are removed by vacuum distillation. The resin, which can beused in electrodeposition coatings, will have a primary carbamateequivalent weight of about 321 g/equ, hydroxy equivalent weight of about272 g/equ, and an acid equivalent weight (not including the weight ofthe salting group) of about 1815 g/equ.

Example 4 Preparation of an Oligomeric Graft Beta or Greater HydroxyCarbamate Polymer According to the Invention for Use in Water-SolubleCoatings

[0163] To a stirred solution of 50 parts of1,3,5-Triazine-2,4,6(1H,3H,5H)-trione and 50 parts of methanol are added70 parts of Jeffamine XTJ-505 (a polyoxylamine from Huntsman ChemicalCorporation, Houston Tex.). The reaction is stirred at room temperatureand followed by amine titration until over 95% of the amine has beenconsumed. Then ammonia gas is bubbled into the reaction mixture. Thereaction is followed by infrared spectroscopy. Once all of the cycliccarbonate groups are consumed, the excess ammonia and solvent areremoved by vacuum distillation. The resin, which can be used forwater-based coatings will have an approximate primary carbamateequivalent weight of 533 g/equ, a hydroxy equivalent weight of 207g/equ. Each oligomer will contain, on average, 10 polyether unitsconnected to the trimer by an urethane link.

Example 5 Preparation of an Urethane Based Resin Backbone (P) Accordingto the Invention

[0164] A solution of 30 parts of anhydrous methyl ethyl ketone and 50parts of N3300 (an aliphatic polyisocyanate based on hexanediisocyanatefrom Bayer, Pittsburgh, Pa.), and 0.07 parts of dibutyl tin dilaurate isheated under an inert atmosphere to 60° C. Then 33.2 parts of4-hydroxymethyl 1,3-dioxane-2-one is added over an one hour period. Thereaction temperature during the addition is allowed to increase to 70°C. After the addition, the reaction mixture is held at 70° C. until allof the hydroxy functional six member cyclic carbonate has beenincorporated. Then 10 parts of i-butanol are added and the reaction heldat 70° C. for an additional hour. The final resin will have a NV ofapproximately 68% and a cyclic carbonate equivalent weight of 333 g/equ(on NV)

Example 6 Preparation of an Urethane Polymer According to the Inventionfor Use in Solvent Based Coatings

[0165] To a solution of 50 parts of the urethane from example 5 and 40parts of methanol is added 6.8 parts of dodecyl amine. The reaction isfollowed by amine titration. Once more than 97% of the amine has beenreacted, ammonia gas is bubbled into the solution. The reaction isfollowed by infrared spectroscopy. Once all of the cyclic carbonategroups are consumed, the excess ammonia and solvent are removed byvacuum distillation. The final product, useful in etch resistantflexible solvent borne coatings will have a primary carbamate equivalentweight of about 641 g/equ and a hydroxy equivalent weight of about 410g/equ.

We claim:
 1. A method of making a multifunctional material, comprisingproviding a material P comprising two or more cyclic carbonate groups(bi) and of the structure:

 wherein n is a number from 0 to 6, q is a number from 2 to 50, and P isa hydrocarbon based material selected from the group consisting ofcompounds, oligomers, and polymers, reacting at least one cycliccarbonate functional group (bi) with ammonia in a reaction (A) toprovide a β or higher-hydroxy primary carbamate group, reacting at leastone cyclic carbonate functional group (bi) with at least one graftingmaterial (c) in a reaction (B) to provide a hydroxyl functionalurethanized grafting moiety, said grafting material (c) comprising atleast one amine group (ci) selected from primary amines, secondaryamines, and mixtures of both primary and secondary amines, and agrafting moiety (cii), wherein the reactions (A) and (B) occursimultaneously or successively.
 2. The method of claim 1 wherein themultifunctional material comprises at least one hydroxyl functionalurethanized grafting moiety and at least one β or higher hydroxy primarycarbamate group.
 3. The method of claim 1 wherein material P is selectedfrom the group consisting of aliphatic materials, cycloaliphaticmaterials, aromatic materials, unsaturated materials, saturatedmaterials, and mixtures thereof.
 4. The method of claim 1 whereinmaterial P is a compound having a number average molecular weight offrom 174 to
 2000. 5. The method of claim 1 wherein material P comprisestwo or more repeating units.
 6. The method of claim 1 wherein material Pis an oligomer having from two to nine repeating units and a numberaverage molecular weight of from 202 to
 1499. 7. The method of claim 5wherein material P is a polymer having ten or more repeating units and anumber average molecular weight of from 1500 to 1,000,000.
 8. The methodof claim 7 wherein material P is a polymer having a number averagemolecular weight of from 1500 to 50,000.
 9. The method of claim 7wherein material P is selected from the group consisting of biurets,isocyanurates, isocyanurates, acrylics, modified acrylics,polyurethanes, polyesters, polylactones, polyureas, alkyds,polysiloxanes, polyethers, epoxy upgrades, and mixtures thereof.
 10. Themethod of claim 1 wherein material P further comprises one or moreoptional functional groups (bii) which are different from cycliccarbonate functional groups (bi) and are essentially inert with respectto the cyclic carbonate functional groups (bi) in the presence ofreactions (A) and (B).
 11. The method of claim 1 wherein n is a numberfrom 0 to
 3. 12. The method of claim 11 wherein n is from 0 to
 1. 13.The method of claim 1 wherein the amine group (ci) is selected fromprimary amines, secondary amines, and mixtures thereof.
 14. The methodof claim 13 wherein the amine group (ci) is a primary amines.
 15. Themethod of claim 1 wherein the grafting moiety (cii) is at least one ofthe group consisting of aliphatics, cycloaliphatics, polyurethaneoligomers and polymers, nonionic groups, polyalkyldienes, triazines,hindered amine light stabilizers, aromatic groups, ionic groups, andmixtures thereof.
 16. The method of claim 15 wherein the grafting moiety(cii) is at least one of the group consisting of aliphatics,cycloaliphatics, polyurethane oligomers and polymers, polyalkyldienes,triazines, aromatic groups, ionic groups, and mixtures thereof.
 17. Themethod of claim 1 wherein reaction (A) and reaction (B) occursimultaneously.
 18. The multifunctional material made by the method ofclaim
 1. 19. A curable coating composition comprising themultifunctional material of claim
 1. 20. A method of making amultifunctional acrylic oligomer or polymer, comprising providing anethylenically unsaturated monomer mixture (a) comprising two or moremonomers (ai) having at least one cyclic carbonate group (bi) and thestructure

 wherein L is a linking group selected from aliphatic groups,cycloaliphatic groups, aromatic groups and mixtures thereof of from oneto seven carbons, n is a number from zero to six, and R is eitherhydrogen or an alkyl group of from one to six carbons, polymerizing themonomer mixture (a) to make an acrylic backbone polymer (b) comprisingtwo or more cyclic carbonate functional groups (bi), subjecting theacrylic backbone polymer (b) to successive or simultaneous reactions ofreaction (A) with a grafting material (c) and reaction (B) with ammonia,to make a multifunctional acrylic oligomer or polymer of the formula:

 wherein A is the residue resulting from the polymerization ofethylenically unsaturated monomers which do not contain a cycliccarbonate group, L is a linking group selected from aliphatic groups,cycloaliphatic groups, aromatic groups and mixtures thereof of from oneto seven carbons, p is number of from 0 to 5, C_(NH3) is the reactionproduct of ammonia with a cyclic carbonate functional group andcomprising a structure selected from the group of formulas (I), (II) and(III):

 wherein C′ is a saturated carbon having substituents selected fromhydrogen and alkyl groups of from one to six carbons, and n is a numberfrom 0 to 6, and C_(graft) is the reaction product of ammonia and acyclic carbonate functional group and comprising at least one structureselected from the group consisting of of formulas (I), (II) and (III):

wherein C′ is a saturated carbon having substituents selected fromhydrogen and alkyl groups of from one to six carbons, R is hydrogen oran alkyl group of from one to six carbons, and c_(ii) is a graftingmoiety selected from aliphatics, cycloaliphatics, polyurethane oligomersand polymers, nonionic groups, polyalkyldienes, triazines, hinderedamine light stabilizers, aromatic groups, ionic groups, and mixturesthereof, k is from 1 to 95% by weight of the total sum of k, l, and m,l, is from 0 to 98% by weight of the total sum of k, l, and m, and m isfrom 1 to 95% by weight of the total sum of k, l, and m.
 21. The methodof claim 20 wherein the monomer mixture (a) further comprises one ormore additional ethylenically unsaturated monomers (aii) havingfunctional groups which are unreactive with the cyclic carbonatefunctional groups of monomer (ai) under free radical polymerizationconditions.
 22. The method of claim 20 wherein monomer mixture (a)further comprises one or more nonfunctional ethylenically unsaturatedmonomers (aiii).
 23. The method of claim 21 wherein the free radicalpolymerization occurs (1) in temperatures of no more than 180 degreesC., (2) in the absence of epoxy catalysts, and (3) in the absence ofcatalysts such as Lewis acids and sulphonic acids having a pKa of lessthan 2.0.
 24. The method of claim 21 wherein the one or moreethylenically unsaturated monomers (aii) are selected from the groupconsisting of hydroxyl functional ethylenically unsaturated monomers,isocyanate functional ethylenically unsaturated monomers, carboxylicacid functional ethylenically unsaturated monomers, urea functionalethylenically unsaturated monomers, carbamate functional ethylenicallyunsaturated monomers, and mixtures thereof.
 25. The method of claim 21wherein the step of polymerizing monomer mixture (a) makes an acrylicbackbone polymer (b) further comprising one or more functional groups(bii) which are unreactive with the cyclic carbonate groups (bi) underfree radical polymerization conditions.
 26. The method of claim 25wherein the functional groups (bii) of acrylic backbone polymer (b) areselected from the group consisting of hydroxyl groups, isocyanategroups, epoxy groups, carboxylic acid groups, carbamate groups, ureagroups, and mixtures thereof.
 27. The method of claim 25 furthercomprising reacting the one or more functional groups (bii) with one ormore compounds (d) to provide a functional group (bii′).
 28. The methodof claim 27 wherein said reaction between functional groups (bii) andcompound (d) occurs before the reaction of the at least one amine group(ci) of the grafting material (c) with the cyclic carbonate functionalgroups (bi) to make an acrylic graft polymer.
 29. The method of claim 20further comprising reacting the hydroxyl group of the urethanizedacrylic graft polymer with one or more compounds (c).
 30. The method of20 wherein the monomer (ai) has the structure

wherein Rn is a straight chain alkane of from 1 to 4 carbons, and R is Hor CH₃.